Surface-active oligomers, a process for their preparation and compositions containing them

ABSTRACT

The invention provides surface-active random oligomers of the general formula: 
     
         R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H               (I) 
    
     in which R 1  denotes a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical or a cyclo-aliphatic, aromatic or alkylaromatic radical containing 1 to 30 carbon atoms, Z denotes a group A and/or at least one group corresponding to the formula (II) 
     
         R.sub.2 --O--C.sub.2 H.sub.3 (A)--O].sub.m CH.sub.2 --     (II) 
    
     in which R 2  denotes a hydrocarbon radical having the meaning indicated for R 1  and containing a number of carbon atoms from 8 to 30, n denotes an average statistical value from 1 to 20, m denotes an average statistical value from 0.5 to 10 and A denotes a group of hydrophilic character. These oligomers can be used in cosmetic or pharmaceutical compositions.

This is a division of application Ser. No. 557,212 filed Dec. 2, 1983now U.S. Pat. No. 4,656,030 which is a division of application Ser. No.285,422 filed July 20, 1981 now U.S. Pat. No. 4,430,250.

The present invention relates to surface-active oligomers, a process fortheir preparation and cosmetic or pharmaceutical compositions in whichthey are present.

A large number of surface-active agents consisting of a lipophilicaliphatic or arylaliphatic hydrocarbon fatty chain joined to ahydrophilic chain are already known. These products have found numerousapplications in the most diverse fields.

It has already been proposed (see French Patent Application No.2,359,165), to replce the single hydrocarbon chain of the conventionalsurface-active agents by a lipophilic sequence obtained by thepolymerisation of an alkylene oxide or a glycidyl ether having a longchain.

More recently, other oligomers in which the distribution of the units oflipophilic character and of the units of hydrophilic character is randomhave been described. In fact, it has been found that these productspossess improved properties compared with those described previously.

These oligomers are prepared using 1,2-epoxides as starting materials,these generally being expensive reactants which are not always availableon an industrial scale and, in certain cases, are very difficult toprepare.

The alkyl glycidyl ethers also proposed as starting materials are evenmore expensive reactants. Moreover, these are compounds of highmolecular weight, which cannot always be easily purified bydistillation.

We have now discovered, according to the present invention, a new familyof products which can be prepared using mixtures of compounds having anoxirane end group and generally containing more than one ether group,which mixtures are much easier to obtain industrially. As these startingmaterials do not need to be purified by distillation, they can be useddirect from the reaction medium.

Apart from their very low industrial cost, these products exhibit theadditional advantage that they can be prepared from any alcohol ormixture of alcohols of high molecular weight, and in particular fromcuts of industrial fatty alcohols.

In the latter case, the corresponding mixtures of alkyl glycidyl etherscan not be purified by distillation without altering their compositions.

Despite the nature of the starting materials used, the products preparedin this way have a generally low aggressiveness towards the skin and themucous membranes of the eye. They can thus be used as additives incosmetic compositions or as excipients in pharmaceutic compositions.

Accordingly, the present invention provides new surface-active oligomersobtained by the random polyaddition, to an alcohol, of, essentially:

(1) a mixture of monoether and polyether compounds having an epoxide endgroup;

(2) an epihalogenohydrin and

(3) if appropriate, small proportions of a bis-epoxide or mixture ofbis-epoxides, acting as a chain extender and/or crosslinking agent.

The invention also provides the process for the preparation of thesecompounds as well as cosmetic or pharmaceutical compositions based onthese compounds.

The surface-active random oligomers according to the present inventionare essentially represented by the following general formula (I):

    R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H               (I)

in which R₁ denotes a linear or branched saturated or unsaturatedaliphatic hydrocarbon radial or a cycloaliphatic, aromatic oralkylaromatic radical containing 1 to 30 carbon atoms, Z denotes a groupA and/or at least once a group corresponding to the formula (II):

    R.sub.2 --O--C.sub.2 H.sub.3 (A)--O].sub.m CH.sub.2        (II)

in which R₂ denotes a hydrocarbon radical having the meaning indicatedfor R₁, containing a number of carbon atoms which can vary from 8 to 30, n denotes any average statistical value from 1 to 20, m denotes anyaverage statistical value from 0.5 to 10 and preferably 0.5 to 5, and Adenotes a group of hydrophilic character, which can, in general, benon-ionic, cationic, anionic or zwitterionic.

A can more particularly denote the following groups: ##STR1## in which udenotes the value 0 or 1. ##STR2##

in which R₃ and R₄, which are identical or different, denote alkyl orhydroxyalkyl radicals containing from 1 to 3 carbon atoms and moreparticularly methyl, ethyl and/or hydroxyethyl groups, or alternativelyR₃ and R₄ form, with the nitrogen atom, a heterocyclic ring having 5 or6 ring members and preferably a piperidino or morpholino group, and udenotes the value 0 or 1. ##STR3## in which HV denotes a mineral ororganic acid such as hydrochloric, hydrobromic, sulphuric, phosphoric,acetic, lactic, citric or tartaric acid u, R₃ and R₄ having the samemeanings as those indicated for the group (c). ##STR4## in which R₅denotes a methyl, ethyl or hydroxyethyl radical, T³¹ denotes an anionsuch as Cl⁻, Br⁻, I⁻, CH₃ SO₃ ⁻, CH₃ SO₄ ⁻ or CH₃ --C₆ H₄ --SO₃ ⁻, u, R₃and R₄ having the same meanings as those indicated for the group of theformula (c). ##STR5## in which Q⁻ denotes a group CH₂ COO⁻, CH₂ --CH₂COO⁻ or (CH₂)₃ SO₃ ⁻, R₃ and R₄ having the same meanings as thoseindicated for the group (c).

    --OSO.sub.3 M                                              (g)

in which M denotes a hydrogen atom or an alkali metal or on euivalent ofan alkaline earth metal preferably sodium, potassium, 1/2 calcium or 1/2magnesium.

    --OCOCH.sub.2 SO.sub.3 M                                   (h)

in which M has the same meaning as that indicated for the group (g).##STR6## in which M has the same meaning as that indicated for the group(g) and u denotes 0 or 1, and also the crosslinked oligomers of theformula (I).

The groups R₁ and R₂ preferably denote linear or branched C₆ to C₂₀alkyl or alkenyl radicals.

The mixture of compounds corresponding to the formula (I) according tothe invention can be obtained from polyhalogenated compoundscorresponding to the formula (III)

    R.sub.1 --O--C.sub.2 H.sub.3 (Y)O--.sub.n H                (III)

in which R₁ and n have the same meaning as that indicated above for theformula (I) and Y denotes the group CH₂ X and/or at least once the groupof the formula (IV)

    R.sub.2 --O--C.sub.2 H.sub.3 (CH.sub.2 X)--O].sub.m CH.sub.2 (IV)

in which R₂ and m have the same meaning as that indicated for theformula (II). X denotes a halogen atom such as bromine or chlorine, andpreferably a chlorine atom.

The intermediates of the formula (III) used for the preparation of themixture of compounds according to the invention can be obtained by thepolyaddition, to one molecule of a compound of the formulae R₁ OH(containing at least one hydroxyl group and serving as an initiator) ofa mixture of n molecules of epoxides, consisting of:

(1) p molecules of products of the general formula (V), p being a numberfrom 1 to 20: ##STR7## in which R₂, X and m have the same meaning asthat indicated for the formula (IV),

(2) (n-p) molecules of an epihalogenohydrin preferably epichlorohydrin,and, if appropriate,

(3) q molecules of a diepoxide compound acting as a chain extender orcrosslinking agent, q being from 0 to 0.05n.

The compounds corresponding to the formula R₁ OH which act as initiatorsor also telogens in the telomerisation reactions making it possible toprepare the compounds according to the invention are alcohols havingfrom 1 to 30 carbon atoms, chosen from the aliphatic, cycloaliphatic oralkylaromatic series. Amongst these alcohols, saturated or unsaturatedC₆ to C₂₀ alcohols may be mentioned in particular.

The epoxides corresponding to the formula (V) are products containingstatistically more than one ether group in addition to the oxirene groupand can themselves be obtained by the polyaddition of (m+1) molecules ofan epihalogenohydrin, preferably epichlorohydrin, to one molecule of analcohol of the formula R₂ OH, in the presence of a Lewis acid catalystsuch as BF₃, SnCl₄ or SbCl₅, at a temperature of, say, 20° to 100° C.,followed by reaction with an alkaline agent such as sodium hydroxide orpotassium hydroxide. The latter reaction, leading to cyclisation, issuitably carried out at 30° to 80° C., with or without a solvent. Thesolvents which can be used are preferably short-chain secondary ortertiary alcohols such as isopropyl or tert.-butyl alcohol. Theresulting products are then washed with water and, if appropriate,neutralised with an acid, such as hydrochloric acid, in order to removeany trace of basicity, and dried by heating under reduced pressure.

The halogenated epoxides thus obtained can be used direct for thepreparation of the intermediates corresponding to the formula (III). Forthis purpose, they are mixed with the epihalogenohydrin and, ifappropriate, the diepoxide, and the mixture is then added progressivelyto the alcohol or to the mixture of alcohols corresponding to theformula R₁ OH, in the presence of a Lewis acid catalyst, typically BF₃,SnCl₄ or SbCl₅, and, if appropriate, a solvent such as an aliphatichydrocarbon, at a temperature of, say, 20° to 100° C., until the oxiranegroups have completely reacted. When a diepoxide is used, this can alsobe introduced after the polyaddition reaction of the epihalogenohydrinand the compounds corresponding to the formula (V).

Diglycidyl ether or the bis-glycidyl ether of bisphenol A may bementioned as diepoxides which can be used according to the invention.

The proportions of catalysts used are generally 0.05 to 5% by weight,relative to the reaction mixture.

The epihalogenohydrin and the epoxides corresponding to the formula (V)are introduced as a mixture. Thus, the distribution of the units of theformula CH₂ X and of the groups of the formula (IV) in the productscorresponding to the formula (III), and consequently that of theresulting units A and (II) in the products of the formula (I) accordingto the invention, is completely random. The relative proportion of thegroup of the formula A and of the group of the formula (II) is that ofthe epoxides used, that is to say ##EQU1##

The preparation of the epoxides corresponding to the formula (V) and theintermediates corresponding to the formula (III) result from reactionsof compounds having an alcohol group with epoxides; consequently, thereare two possible structures for the various units, according to the twodirections of opening of the epoxide group.

Thus, for the compounds corresponding to the formula (V), theconfiguration of the unit in brackets represents isomeric structures:##STR8## and the same applies to the compounds corresponding to theformula (III) as regards the group [C₂ H₃ (Y)--O], which represents:##STR9## and, in the formula (I), to --C₂ H₃ (Z)O--, which representsthe following two structures: ##STR10##

Nevertheless, for the products according to the invention, the isomersrepresented by the formulae (Va), (IIIa) and (Ia) are predominant.

The products corresponding to the formula (III) are subsequentlyconverted to products of the formula (I) according to the invention,under various conditions, depending on the nature of the group A and Z,if appropriate after the volatile compounds have been removed bymolecular distillation.

(a) When A denotes --CH₂ OH, the replacement of the halogen atoms in thecompounds of the formula (III) by hydroxyl groups can be carried out byreaction with an alkali metal salt of a carboxylic acid, and preferablywith sodium acetate or potassium acetate, at a temperature of, say, 150°to 200° C., in a suitable solvent advantageously a glycol or glycolderivative; the acetic acid ester formed is then saponified by means of,say, sodium hydroxide or potassium hydroxide or alcoholysed by means ofa lower alcohol such as methanol or ethanol, in the presence of a basiccatalyst preferably sodium methylate or ethylate or potassium methylateor ethylate. This process is described in greater detail in U.S. Pat.No. 3,518,719.

(b) When A denotes the groups: ##STR11## the replacement of the halogenatoms of the halogenopropoxy unit by thiohydroxyethyl groupscorresponding to the formula:

    --S--CH.sub.2 --CH.sub.2 OH

or thiodihydroxypropyl groups:

    --S--CH.sub.2 --CHOH--CH.sub.2 OH

can be carried out by heating the intermediate of the formula (III) with2-mercaptoethanol or 3-mercaptoglycerol, at a temperature of, say, 20°to 150° C., in the presence of an alkali metal compound, advantageouslythe hydroxide, methylate or ethylate of sodium or potassium, andpreferably in the presence of a solvent such as an alcohol, glycol etheror polyglycol and, if appropriate, water.

The halogen substitution reaction can then be followed, if appropriate,by an oxidation reaction preferably carried out with hydrogen peroxideat a temperature of, say, 0° to 50° C. and preferably 30° to 40° C., inroughly stoichiometric proportions and advantageously in the presence ofacetic acid. This process is described in greater detail in U.S. Pat.No. 3,906,048.

(c) When A denotes: ##STR12## the compounds of the formula (I) can beobtained by heating the intermediate halogen compounds corresponding tothe formula (III) with a secondary amine corresponding to the formula:##STR13## in which R₃ and R₄ have the same meaning as that indicatedabove, if appropriate in the presence of a solvent, particularly aglycol or alkoxyethanol, at atmospheric pressure or in an autoclave, ata temperature of, say, 50° to 160° C. The products are then oxidised, ifappropriate, with hydrogen peroxide or a per-acid such as peracetic orperformic acid, at temperatures of, say, 10° to 100° C.

(d) The compounds corresponding to the formula (I) in which A denotes agroup corresponding to the formula: ##STR14## can be obtained bysalifying the above compounds with a mineral or organic acid, preferablyhydrochloric, hydrobromic, sulphuric, phosphoric, acetic, lactic, citricor tartaric acid, if appropriate in the presence of a solvent,especially an alcohol having, more particularly, 1 to 4 carbon atoms, toensure the homogeneity of the reaction medium. (e) The compoundscorresponding to the formula (I) according to the invention in which Adenotes: ##STR15## can be obtained from the compounds corresponding tothe formula (I) in which A, forming part of Z, denotes the groupcorresponding to the formula (c), by alkylation with a compound of theformula R₅ T, in which T and R₅ have the meanings indicated above, thiscompound preferably being methyl or ethyl chloride, bromide, iodide,sulphate, mesylate or tosylate or glycol chlorohydrin.

The alkylation reactions can be carried out with or without a solvent,typically an alcohol, or ether-alcohol, if appropriate in the presenceof water, a chlorinated solvent or an aromatic solvent, at temperaturesof, say, 10° to 80° C.

(f) The compounds corresponding to the formula (I) according to theinvention in which A represents a group of the formula: ##STR16## can beobtained from the compounds in which A denotes: ##STR17## by alkylationwith methyl or ethyl chloroacetate or chloropripionate, followed bysaponification either with sodium chloroacetate or chloropropionate orpotassium chloroacetate or chloropropionate, or alternatively withpropane-sultone if Q⁻ denotes the propylsulphonate anion.

(g) The compounds corresponding to the formula (I) in which A denotesthe group --OSO₃ M can be obtained by sulphation of the compounds of theformula (I) in which A denotes the group --CH₂ OH, with chlorosulphonicacid, if appropriate in the presence of a solvent, preferablychloroform, dichloroethane, benzene or toluene. If M denotes an alkalimetal or one equivalent of an alkaline earth metal, the acid obtained isneutralised with the corresponding base.

(h) The compounds of the formula (I) in which A denotes the group

    --OCOCH.sub.2 SO.sub.3 M

can be obtained by esterification of a compound corresponding to theformula (I) in which A denotes the group --CH₂ OH, with sulphoaceticacid, the acid formed being neutralised, if appropriate, with an alkalimetal base or alkaline earth metal base.

(i) The compounds of the formula (I) in which A denotes the group##STR18## can be obtained by reacting the intermediate halogen compoundsof the formula (III) with methyl or ethyl thioglycolate in the presenceof sodium methylate or potassium methylate and an alcohol having 1 to 4carbon atoms, acting as a solvent, at a temperature of, say, 80° to 120°C., this being followed, if u denotes 1, by oxidation with hydrogenperoxide or a per-acid.

The resulting ester is saponified and acidified to obtain thecorresponding acid. The alkali metal salt can be obtained byneutralising the acid with corresponding base.

The mixtures of compounds of the formula (I) according to the presentinvention are generally in the form of viscous oils or pastes which aresoluble or dispersible in water. These compounds usually have amolecular weight of 500 to 5,000.

We have discovered that these compounds can be used in variousindustries as surface-active agents, especially as low-foaming agents,as as wetting agents, detergents, peptising agents, dispersants, bindersand anti-caking agents, as solubilising agents, penetrating agents,anti-redeposition agents and flotation agents, as antistatic finishesand as dyeing assistants.

The compositions of the present invention generally contain at least0.2% by weight of a mixture of compounds corresponding to the formula(I). The proportion of the mixture of compounds of the formula (I) inthe compositions can range up to, say, 80% by weight.

The compositions are generally aqueous or aqueous-alcoholiccompositions, the alcohols being lower alcohols or alcohols based onglycol ethers.

We have noted more particularly that the compounds corresponding to theformula (I) possess a low aggressiveness towards the skin and the mucousmembranes and that their properties are particularly valuable when theyare used in cosmetic compositions or pharmaceutical compositions.

The invention thus also provides pharmaceutical or cosmetic compositionswhich are essentially characterised in that they contain at least onemixture of surface-active oligomers of this invention. The cosmeticcompositions can include, in particular, compositions for the care ofthe skin, nails or hair.

In general, the cosmetic or pharmaceutical compositions according to theinvention can be presented in various forms, such as in the form ofaqueous, alcoholic or aqueous-alcoholic solutions, in the form of acream, gel or emulsion or in the form of which it is packaged in anaerosol.

They usually contain the mixture of compounds corresponding to theformula (I) in amounts of 0.2 to 80% by weight, and advantageously 0.5to 50%. by weight, relative to the total weight of the composition. Themixture of compounds of the formula (I) can be used, in particular, asthe only surface-active agents or in a mixture with other surface-activecompounds of the anionic, cationic, non-ionic or amphoteric type.

The compositions can also contain alkalising or acidifying agents, foamsynergistic agents, foam stabilisers, thickeners, opacifiers,sequestering agents, superfatting agents, antiseptics, preservatives,anionic, cationic, non-ionic or amphoteric polymers or mixtures thereof,pigments, perfumes, dyestuffs, agents for imparting pearlescence,solvents, sun filters, oxidising agents, reducing agents, electrolytes,oils, waxes, natural substances, protein derivatives, antiserborrheicagents, anti-dyestuff agents and also may other active substance whichcan have an action in the treatment, care or protection of the skin orhair, and any adjuvants normally used in cosmetic compositions.

Acids and bases can be used in amounts appropriate for adjusting the pHof the compositions to, say, 3 to 12 and preferably 3 to 10.

Apart from the active substances for the treatment of the human oranimal body and the oligomers according to the invention, thepharmaceutical compositions can contain pharmaceutically acceptableexcipients.

For hair care, the compositions containing the compounds according tothe invention can be, for example, shampoos, hair-conditioningcompositions or dyeing compositions.

In addition to the mixture of random surface-active oligomers accordingto the invention, the shampoos can contain one or more anionic,cationic, amphoteric or non-ionic surface-active agents or a mixturethereof, and also other cosmetic adjuvants normally used in this type ofcomposition.

The dyeing compositions can be based on so-called oxidation dyestuffprecursors or so-called direct dyestuffs or mixtures thereof.

Depending on the nature of the components, the compositions according tothe invention can also be used as lotions for rinsing the hair, fluidmilks for the body, moisturising creams, lipsticks, eye shadows,wavesetting lotions and lacquers, and also for other cosmeticapplications, these compositions always containing at least thesurface-active random oligomers according to the invention.

The following Examples further illustrate the present invention.

EXAMPLE 1 Preparation of a mixture of compounds of the general formula(I) in which

R₁ denotes C₁₂ H₂₅, n=10 and Z denotes, in the proportions ##EQU2## CH₂OH and the group of the formula II in which: R₂ denotes C₁₂ H₂₅, A=CH₂OH and m=0.5.

(a) Preparation of the epoxide compounds of the formula V in which R₂and m have the meaning indicated above and X denotes Cl.

1.2 ml of BF₃ etherate are added to 278 g (1.5 mols) of dodecan-1-olsold under the trade name Alfol 12, and 208 g (2.25 mols) ofepichlorohydrin are then added, at 50° C., in the course of 1 hour 15minutes.

The temperature and the stirring are maintained for a further 15minutes. A slightly yellow, viscous liquid with an epoxide number ofzero is thus obtained.

475 g of t-butanol are added and 265 g of 40% strength sodium hydroxidesolution are then added, at 50° C., in the course of 20 minutes, under anitrogen atmosphere. After the mixture has been stirred for 1 hour at50°-60° C., it is washed with 900 ml of hot water and then a furthertwice with 500 ml.

After the solvents have been evaporated off under reduced pressure, avirtually colourless liquid with an epoxide number of 3.3milliequivalents/g and an organic chlorine number of 1.9milliequivalents/g is obtained.

(b) Preparation of the mixture of intermediates of the formula III inwhich R₁, n, R₂, m and X have the meanings indicated above.

0.25 ml of BF₃ etherate is added to 18.6 g (0.1 mol) of Alfol 12, and amixture of 64.7 g (0.7 mol) of epichlorohydrin and 90.5 g (0.3equivalent of epoxide) of compounds obtained in Example 1(a) above isthen added, at 60° C., in the course of 1 hour 45 minutes. During theaddition of the mixture of epoxide compounds, 0.52 ml of BF₃ is added inportions.

The temperature and the stirring are maintained for 30 minutes after theaddition has ended.

The epoxide number of the reaction mixture is virtually zero.

(c) Preparation of the compounds of the formula I defined above.

170 g of diethylene glycol butyl ether (B.D.G.) and 86.2 g of potassiumacetate are added to 172 g (0.86 equivalent of chlorine) of productobtained above, and the mixture is heated at 180° C. for 6 hours. Theextent of reaction, measured by determining the chloride ions, is about98%.

95 g of 40% strength sodium hydroxide solution and 100 ml of water arethen added in the course of 45 minutes and the mixture is subsequentlystirred at 40°-50° C. for 30 minutes to 1 hour. The reaction mixture isthen neutralised with hydrochloric acid.

The organic phase is then separated off by decantation and the solventsare subsequently removed by heating under reduced pressure.

After the inorganic salts have been filtered off, a deep brown oil isobtained which is dispersible in water and soluble in vaseline oil.

The cloud point, measured at a concentration of 5% in butyldiglycol(B.D.G.) containing 25% of water, is 44° C.

EXAMPLE 2 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes a mixture of C₈ H₁₇ and C₁₀ H₂₁ radicals, n=9 and Z denotes,in the proportions ##EQU3## the group CH₂ OH and the group of theformula II in which: R₂ denotes C₈ H₁₇ and C₁₀ H₂₁, A=CH₂ OH and m=0.5.

(a) Preparation of the epoxide compounds of the formula V in which R₂and m have the meaning indicated above and X denotes Cl.

1 ml of BF₃ etherate is added to 215 g (1.5 mols) of Alfols 8/10, and208 g (2.25 mols) of epichlorohydrin are then added, at 50° C., in thecourse of 1 hour 30 minutes.

The product obtained is taken up with 210 g of t-butanol, and 225 g of40% strength sodium hydroxide solution are then added in the course of30 minutes at 50°-60° C. After stirring for 1 hour, the reaction mixtureis washed 3 times with respectively 600, 400 and 400 ml of hot water.

After drying, 360 g of a product are obtained in the form of a virtuallycolourless liquid.

N_(epoxide) : 3.9 milliequivalents/g

N_(Cl) : 2.0 milliequivalents/g

(b) Preparation of the mixture of intermediates of the formula III inwhich R₁, n, R₂, m and X have the meanings indicated above.

0.37 ml of BF₃ etherate is added to 14.3 g (0.1 mol) of Alfols 8/10, and77 g (0.3 equivalent of epoxide group) of compounds obtained in theabove example and 55.5 g (0.6 mol) of epichlorohydrin are then added, at50° C., in the course of 1 hour 30 minutes.

(During the addition of the epoxide, a further 0.15 ml of BF₃ is added.)After stirring for a further 1 hour at 50° C., the epoxide number isvirtually zero.

(c) Preparation of the compounds of the formula I defined above.

144.5 g of product obtained in this way are dissolved in 145 g of B.D.G.and, after the addition of 76 g (0.77 mol) of potassium acetate, thesolution is then heated for 5 hours 30 minutes at 180° C.

It is left to cool to 50° C. and 152 g of 20% strength sodium hydroxidesolution are then added in the course of 30 minutes.

After stirring for 1 hour 30 minutes, the mixture is diluted with 150 mlof hot water, any alkalinity is neutalised with hydrochloric acid, andthe organic phase is decanted and then dried by heating under reducedpressure.

After the residual inorganic salts have been filtered off at 80° C., athick water-dispersible oil having a cloud point in B.D.G. of 51° C. isobtained.

EXAMPLE 3 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes a mixture of C₁₆ H₃₃ and C₁₈ H₃₇ radicals, n=5 and Z denotesthe group of the formula II in which: R₂ denotes ##STR19## A=CH₂ OH andm=3.

(a) Preparation of the compounds of the formula V in which R₂ and m havethe above meaning and X denotes Cl.

0.76 ml of BF₃ etherate is added to 121 g (0.5 mol) of 2-hexyldecanol,and 185 g (2 mols) of epichlorohydrin are then added, at 50° C., in thecourse of 1 hour 30 minutes.

After stirring for a further 1 hour, 155 g of t-butyl alcohol are addedand 75 g of 40% strength NaOH solution are then added at 50° C.

The stirring and heating are maintained for 1 hour. The organic phase isthen washed 3 times with 400 ml of hot water and dried by heating underreduced pressure.

260 g of a product with an epoxide number of 1.53 milliequivalents/g anda chlorine number of 5.3 milliequivalents/g are thus obtained.

(b) Preparation of the mixture of intermediates of the formula III inwhich R₁, n, R₂, m and X have the meaning indicated above.

0.22 ml of BF₃ is added to 6.5 g (0.025 mol) of a mixture of hexadecanoland octadecanol with a hydroxyl number of 3.8 milliequivalents/g, and81.7 g (0.125 equivalent of epoxide groups) of compound obtained inExample 3(a) above are then added in the course of 1 hour 30 minutes at50° C.

After stirring for 1 hour at 50° C., the reaction is virtually complete.

(c) Preparation of the compounds of the formula I indicated above.

The product obtained above is taken up in 90 g of dipropylene glycol.43.5 g of potassium acetate are then added and the mixture is heatedunder a nitrogen atmosphere for 5 hours 30 minutes at 180° C.

The inorganic salts are filtered off and the solvent is distilled underreduced pressure.

The residual mixture is solubilised in 80 g of absolute ethanol andthen, after the addition of 0.7 g of sodium methylate containing 5.8milliequivalents/g, the mixture is left to stand overnight at ambienttemperature.

The product obtained after distillation of the solvent is in the form ofa thick brown oil which is sparingly soluble in water and soluble invaseline oil.

EXAMPLE 4 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes a mixture of branched C₁₄, C₁₆ and C₁₈ alkyl radicals, n=4and Z denotes the group of the formula II in which: R₂ =C₁₂ H₂₅, A=CH₂OH and m=2.

(a) Preparation of epoxide compounds of the formula V in which R₂ and mhave the above meaning and X denotes Cl.

1.15 ml of BF₃ etherate are added to 186 g (1 mol) of dodecan-1-ol, and277.5 g (3 mols) of epichlorohydrin are then added, at 50° C., in thecourse of 1 hour 30 minutes.

After stirring for 1 hour, 230 g of t-butyl alcohol are added and 150 gof 40% strength sodium hydroxide solution are then added in the courseof 20 minutes.

The stirring and heating are maintained for 1 hour and the reactionmixture is then washed 3 times with 500 ml of hot water.

The product obtained after heating under reduced pressure is in the formof a viscous liquid with an epoxide number of 2.2 milliequivalents/g anda chlorine number of 4.9 milliequivalents/g.

(b) Preparation of the mixture of intermediates of the formula II inwhich R₁, n, R₂, m and X have the meanings indicated above.

0.2 ml of BF₃ etherate is added to 10 g (0.037 mol) of a mixture ofbranched C₁₄, C₁₆ and C₁₈ alcohols sold under the trade name Sidopol bySidobre Sinnova and having a hydroxyl number of 3.7 milliequivalents/g,and 68.5 g (0.15 equivalent of epoxide groups) of the product obtainedin accordance with Example 4(a) above are then added, at 50° C., in thecourse of 1 hour 30 minutes.

(c) Preparation of the compound of the formula I indicated above.

After heating for a further 1 hour, the reaction mixture obtained instep (b) of Example 4 is taken up with 80 g of dipropylene glycol, inthe presence of 35 g of potassium acetate, and the mixture is heated for5 hours 30 minutes at 180° C.

The inorganic salts are filtered off and the solvent is removed byheating under reduced pressure.

The residue is solubilised in 75 g of absolute ethanol and the solutionis left to stand overnight at ambient temperature, in the presence of0.6 g of sodium methylate. After the solvent has been evaporated off, aproduct is obtained in the form of a thick brown oil which is sparinglysoluble in water and soluble in vaseline oil.

EXAMPLE 5 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes a mixture of C₈ H₁₇ and C₁₀ H₂₁ radicals, n=9 and Z denotes,in the proportions ##EQU4## the group CH₂ --OSO₃ Na and the group of theformula II in which: R₂ =C₈ H₁₇ and C₁₀ H₂₁, A=CH₂ --OSO₃ Na and m=0.5.

20 ml of chloroform are added to 23 g (0.5 equivalent of hydroxylgroups) of compounds obtained in accordance with Example 2(c), and 17.5g (0.15 mol) of chlorosulphonic acid are then added dropwise, at 15°-17°C., under a stream of dry nitrogen, in the course of 30 minutes.

The reaction medium thickens during the addition.

It is diluted by adding 10 ml of chloroform.

The mixture is heated progressively to 60° C. and the solvent and thehydrochloric acid formed are then removed under reduced pressure.

After neutralisation with sodium hydroxide in the presence ofisopropanol, and after the inorganic salts have been filtered off, thesolvent is removed by heating under reduced pressure. A water-solublebrown paste is thus obtained.

EXAMPLE 6 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes radicals of lanolin alcohols, n=14 and Z denotes, in theproportions ##EQU5## and the group of the formula II in which R₂=radicals of lanolin alcohols, ##STR20##

(a) Preparation of the epoxide compounds of the formula V in which R₂and m have the meanings indicated above and X denotes Cl.

1.7 ml of BF₃ etherate are added to 300 g (0.72 equivalent of hydroxylgroups) of lanolin alcohols sold under the name Satulan, and 133 g (1.44mols) of epichlorohydrin are then added dropwise, at 55° C., in thecourse of 1 hour 30 minutes. After stirring for 1 hour, the reactionmixture is taken up with 300 g of t-butanol, and 100 g of 40% strengthsodium hydroxide solution are then added in the course of 30 minutes.After stirring for 30 minutes at 50°-60° C., the organic phase is washedwith twice 800 ml of water at 70° C. After distillation under reducedpressure, a light yellow paste with an epoxide number of 2.0milliequivalents/g is obtained.

(b) Preparation of the mixture of intermediates of the formula III inwhich R₁, n, R₂, m and X have the meanings indicated above.

0.63 ml of BF₃ etherate is added to 40.6 g (0.1 equivalent of hydroxylgroups) of Satulan, and a mixture of 100 g (0.2 equivalent of epoxidegroups) of compounds obtained in accordance with Example 6(a) above and111 g (1.2 mols) of epichlorohydrin is then added at 70° C. The additionlasts 3 hours. During the addition, 0.63 ml and 0.25 ml of BF₃ areadded.

The temperature is maintained for a further 1 hour after the additionhas ended.

After cooling, a paste with glints of fluorescent green is obtained.

(c) Preparation of the compounds of the formula I indicated above.

50 g (0.66 mol) of N-methylethanolamine are added to 50 g (0.27equivalent of chlorine) of product obtained in accordance with Example6(b) above, and the mixture is then heated for 3 hours, at 140° C.,under a nitrogen atmosphere.

The reaction mixture is washed 3 times with 100 ml of water at 90° C.,in the presence of 20 ml of n-butanol for the first decantation. Afterdrying under reduced pressure, a light brown paste which is soluble inwater above 56° C. is obtained. Base number: 3.5 milliequivalents/g.

EXAMPLE 7 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes radicals of lanolin alcohols, n=14 and Z denotes, in theproportions ##EQU6## and the group II in which: R₂ =radicals of lanolinalcohols, ##STR21##

25 ml of water and 6 ml of hydrogen peroxide of 130 volumes strength areadded, at 40°-50° C., in the course of 1 hour, to 20 g (0.7 basicequivalent) of compounds obtained in accordance with Example 6(b).

The concentrations of the solution is adjusted to 35% and the solutionis then left to stand for 48 hours at ambient temperature.

The thick light yellow solution thus obtained is soluble in water with avery slight opalescence.

EXAMPLE 8 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes radicals of lanolin alcohols, n=14 and Z denotes, in theproportions 6/1, ##STR22## and the group of the formula II in which: R₂denotes radicals of lanolin alcohols, ##STR23## and m=1.

(a) Preparation of the mixture of compounds of the formula I definedabove, in which u=0.

100 g of methoxyethanol and 32.3 g (0.27 equivalent) of thioglycerol areadded to 50 g (0.27 equivalent of chlorine) of compounds obtained inaccordance with Example 6(b). The mixture is heated at 60° C. under anitrogen atmosphere and 27 g of 40% strength sodium hydroxide solutionare added dropwise in the course of 45 minutes. After the addition, themixture is heated for a further 2 hours 30 minutes at 90° C. The wateris removed by distillation and the sodium chloride is filtered off. Thefiltrate is then evaporated to dryness.

A water-soluble light chestnut paste is thus obtained.

Thioether number: 3.4 milliequivalents/g.

(b) Preparation of the mixture of compounds of the formula I definedabove, in which u=1.

36 g of product obtained in accordance with Example 8(a) above aredissolved in 100 ml of water. 0.6 g of acetic acid is added and 6.9 mlof hydrogen peroxide of 200 volumes strength are then added dropwise at35° C.

A slightly opalescent, light brown solution is obtained.

EXAMPLE 9 Preparation of a mixture of compounds of the general formula Iin which

R₁ denotes radicals of lanolin alcohols, n=14 and Z denotes, in theproportions 6/1, SCH₂ COONa and the group of the formula II in which: R₂denotes radicals of lanolin alcohols, A=--S--CH₂ --COONa and m=1.

100 g of methoxyethanol and 32.6 g (0.27 mol) of ethyl thioglycolate areadded to 50 g (0.27 equivalent of chlorine) of compounds obtained inaccordance with Example 6(b), and 46 g of sodium methylate in methanol(0.27 equivalent) are then added, at 60° C., under nitrogen.

After heating for 1 hour at 60° C., the mixture is heated progressivelyto 95° C., the methanol being removed, and this temperature ismaintained for 2 hours.

The sodium chloride is filtered off and the ester groups are saponifiedby adding 27 g of 40% strength sodium hydroxide solution.

After distillation of the solvents, a water-soluble brown paste isobtained.

EXAMPLE 10

The following dyeing composition is prepared:

    ______________________________________                                        Oxyethyleneated nonylphenol containing 4 mols                                                           22     g                                            of ethylene oxide (EO)(per mole of phenol)                                    Oxyethyleneated nonylphenol containing 9 mols                                                           22     g                                            of ethylene oxide                                                             Propylene glycol          10     g                                            Ethyl alcohol             8      g                                            Compounds of Example 9    2      g                                            Sodium salt of diethylenetriaminepenta-                                                                 2.4    g                                            acetic acid                                                                   35° Be strength sodium bisulphite solution                                                       1.3    g                                            22° Be strength ammonia solution                                                                 10.2   g                                            Hydroquinone              0.15   g                                            Para-aminophenol          0.1    g                                            Para-phenylenediamine     0.1    g                                            Meta-aminophenol          0.05   g                                            Resorcinol                0.15   g                                            Distilled water q.s.p.    100    g                                            ______________________________________                                    

This composition, diluted with an equal weight of hydrogen peroxide of20 volumes strength, gives a gel which is applied to a deep blond headof hair for 30 minutes. After rinsing, shampooing and drying, apearlescent light blond coloration is obtained.

EXAMPLE 11

The following dyeing composition is prepared:

    ______________________________________                                        Lauryl diethanolamide      5      g                                           Sodium salt of sulphated oxyethyleneated                                                                 20     g                                           lauryl alcohol, containing 30% of active                                      ingredient                                                                    Compounds of Example 6     5      g                                           Hydroxyethylcellulose      1      g                                           2-Ethoxyethanol            10     g                                           2-[N--(β-hydroxyethyl)-amino]-5-hydroxy-                                                            0.4    g                                           nitrobenzene                                                                  3-[N--(β-hydroxyethyl)-amino]-4-[N--(β-hydroxy-                                                0.15   g                                           ethyl)-amino]-nitrobenzene                                                    Citric acid q.s.p.         pH 9                                               Distilled water q.s.p.     100    g                                           ______________________________________                                    

This composition is in the form of a slightly thickened liquid which isapplied to a deep blond head of hair for 20 minutes. After rinsing anddrying, the hair possesses a coppery red sheen.

EXAMPLE 12

The following composition is prepared:

    ______________________________________                                        Compounds of Example 2        0.7 g                                           Sodium salt of sulphated alkanol (C.sub.12 -C.sub.14)                                                      40.0 g                                           oxyethyleneated with 2.2 mols of ethylene                                     oxide, containing 25% of active ingredient                                    Cycloimidazoline derivative of coconut oil,                                                                25.0 g                                           sold by MIRANOL under the name MIRANOL C 2 M                                  CONC                                                                           ##STR24##                                                                    R = copra,                                                                    as a solution containing 40% of active ingredient                             Copra diethanolamide          2.0 g                                           Hydrochloric acid q.s.       pH 7.4                                           Water, dyestuff, preservative, perfume q.s.p.                                                               100 g                                           ______________________________________                                    

This composition is used as a shampoo.

EXAMPLE 13

The following composition is prepared:

    ______________________________________                                        Compounds of Example 9     0.5    g                                           Glucoside alkyl ether sold under the name                                                                24.0   g                                           TRITON CG 110 by SEPPIC as a solution con-                                    taining 30% of active ingredient                                              Surface-active agent of the formula:                                                                     5.0    g                                           R--CHOH--CH.sub.2 OH(CH.sub.2 --CHOH--CH.sub.2 --O).sub.n H                   R = mixtures of C.sub.9 -C.sub.12 alkyl radicals and                          n = 3.5 (statistical average value)                                           Polysorbate 20 [polyoxyethylene (20)                                                                     2.0    g                                           sorbitan monolaurate] sold by ATLAS under                                     the name TWEEN 20                                                             Sodium hydroxide q.s.      pH 6                                               Water, dyestuff, preservative, perfume, q.s.p.                                                           100    g                                           ______________________________________                                    

This composition is used as a shampoo.

EXAMPLE 14

The following composition is prepared:

    ______________________________________                                        Compounds of Example 6     1.0     g                                          Triethanolamine alkyl(C.sub.12 -C.sub.14)-sulphate                                                       25.0    g                                          containing 40% of active ingredient                                           C.sub.12 -C.sub.14 alcohol oxyethyleneated with 10 mols                                                  4.5     g                                          of ethylene oxide and carboxymethylated,                                      sold under the name AKYPO RLM 100 by Chem'Y                                   (active ingredient)                                                           Sodium hydroxide q.s.      pH 8.6                                             Water, dyestuff, preservative, perfume, q.s.p.                                                           100     g                                          ______________________________________                                    

This composition is used as a shampoo.

EXAMPLE 15

The following composition is prepared:

    ______________________________________                                        Compounds of Example 2   1.9     g                                            Mixture of cetyl/stearyl alcohol and                                                                   3.0     g                                            oxyethyleneated cetyl/stearyl alcohol con-                                    taining 15 mols of ethylene oxide                                             Hydroxyethylcellulose sold under the name                                                              0.4     g                                            Cellosize QP 4400 H                                                           Distearyldimethylammonium chloride                                                                     0.4     g                                            Sodium hydroxide q.s.    pH 6.7                                               Water, dyestuff, preservative, perfume, q.s.p.                                                         100     g                                            ______________________________________                                    

This composition is used as a lotion for rinsing the hair.

EXAMPLE 16

The following composition is prepared:

    ______________________________________                                        FLUID MILK FOR THE BODY                                                       ______________________________________                                        Compounds of Example 3                                                                              10 g                                                    Isopropyl myristate   40 g                                                    Preservative          qs                                                      Antioxidants          qs                                                      Perfume               qs                                                      Sterile demineralised water q.s.p.                                                                  100 g                                                   ______________________________________                                    

EXAMPLE 17

The following composition is prepared:

    ______________________________________                                        MOISTURISING CREAM                                                            ______________________________________                                        Compounds of Example 3                                                                              5 g                                                     Glycerol monostearate 5 g                                                     Amerchol L 101        5 g                                                     Cetiol LC             30 g                                                    Sodium lactate        3 g                                                     Antioxidants          qs                                                      Preservatives         qs                                                      Perfume               qs                                                      Sterile demineralised water q.s.p.                                                                  100 g                                                   ______________________________________                                    

EXAMPLE 18

The following composition is prepared:

    ______________________________________                                        LIPSTICK                                                                      ______________________________________                                        Compounds of Example 3                                                                            14 g                                                      Indopol H 300       14 g                                                      Stellanol M 32      15 g                                                      Miglyol 810         19 g                                                      Jojoba oil          12 g                                                      Argobase            3.5 g                                                     New Mekon White wax 10 g                                                      Syncrowax E.R.L.C.  2.5 g                                                     Antioxidants        qs                                                        Dyestuff and pigments                                                                             qs                                                        Perfume q.s.        100 g                                                     ______________________________________                                    

EXAMPLE 19

The following composition is prepared:

    ______________________________________                                        MOISTURISING CREAM                                                            ______________________________________                                        Compounds of Example 4                                                                               5 g                                                    Glycerol monostearate 10 g                                                    Sweet-almond oil      30 g                                                    Octyloxyglyceryl palmitate                                                                          10 g                                                    Antioxidants          qs                                                      Preservatives         qs                                                      Perfume               qs                                                      Sterile demineralised water q.s.p.                                                                  100 g                                                   ______________________________________                                    

EXAMPLE 20

The following composition is prepared:

    ______________________________________                                        EYE SHADOW                                                                    ______________________________________                                        Talc                    23.65  g                                              Titanium oxide          15     g                                              Manganese violet        1.20   g                                              Black iron oxide        0.3    g                                              Ferric blue             0.8    g                                              Mica                    40     g                                              Bismuth oxychloride     4      g                                              Vaseline oil            10     g                                              Isopropyl myristate     1.5    g                                              Compounds of Example 4  1.9    g                                              Oleyl alcohol           1.5    g                                              Calcium stearate        0.1    g                                              B.H.A.                  0.05   g                                              ______________________________________                                    

EXAMPLE 21

The following composition is prepared:

    ______________________________________                                        LIQUID REDUCER FOR PERMANENT WAVING                                           ______________________________________                                        Ammonium thioglycolate      9.5    g                                          Ammonium thiolactate solution (50% strength)                                                              4.0    g                                          Ammonium solution (20% strength)                                                                          2.0    g                                          Ammonium bicarbonate        7.0    g                                          Sequestering agent          0.2    g                                          Surface-active oligomers of Example 2                                                                     1.0    g                                          Oxyethyleneated fatty alcohol (20 EO)                                                                     1.0    g                                          Perfume, opacifier, dyestuff, deionised water                                                             100    ml                                         q.s.p.                                                                        ______________________________________                                    

EXAMPLE 22

The following composition is prepared:

    ______________________________________                                        LIQUID REDUCER FOR PERMANENT WAVING                                           ______________________________________                                        Thioglycolic acid           7.0    g                                          Ammonia solution (20% strength)                                                                           6.5    g                                          Ammonium bicarbonate        6.0    g                                          Sequestering agent          0.2    g                                          Surface-active oligomers of Example 9                                                                     0.5    g                                          Oxyethyleneated fatty alcohol (20 EO)                                                                     1.0    g                                          Perfume, opacifier, dyestuff, deionised                                                                   100    ml                                         water q.s.p.                                                                  ______________________________________                                    

EXAMPLE 23

The following composition is prepared:

    ______________________________________                                        LIQUID OXIDISER OR FIXER FOR                                                  PERMANENT WAVING                                                              ______________________________________                                        Hydrogen peroxide      8      volumes                                                                       strength                                        Stabilisers            0.2    g                                               Surface-active oligomers of Example 6                                                                0.5    g                                               Oxyethyleneated nonylphenol (9 EO)                                                                   1.0    g                                               Perfume, opacifier, dyestuff, deionised                                                              100    ml                                              water q.s.p.                                                                  ______________________________________                                    

EXAMPLE 24

The following composition is prepared:

    ______________________________________                                        Compounds of Example 6                                                                             0.2 g                                                    PVP/VA E 735         1.5 g                                                                         (active ingredient)                                      Ethyl alcohol q.s.p. 50° strength                                      Water q.s.p.         100 cc                                                   ______________________________________                                    

The composition is very slightly opalescent.

EXAMPLE 25

The following composition is prepared:

    ______________________________________                                        Compounds of Example 9                                                                             0.3 g                                                    PVP/VA E 735         1 g                                                                           (active ingredient)                                      Ethyl alcohol q.s.p. 10° strength                                      Water q.s.p.         100 cc                                                   ______________________________________                                    

The composition is very slightly opalescent.

EXAMPLE 26

The following composition is prepared:

    ______________________________________                                        Compounds of Example 6                                                                             0.2 g                                                    PVP/VA E 735         1.5 g                                                                         (active ingredient)                                      Gafquat 734          0.5 g                                                                         (active ingredient)                                      Ethyl alcohol q.s.p. 50° strength                                      Water q.s.p.         100 cc                                                   ______________________________________                                    

The composition is very slightly opalescent.

The compositions of Examples 24, 25 and 26 are used as leave-onwavesetting lotions.

In these examples, PVP/VA E 735 denotes a vinylpyrrolidone/vinyl acetate(70/30) copolymer.

EXAMPLE 27

The following composition is prepared:

    ______________________________________                                        Compounds of Example 2                                                                             0.2 g                                                    PVP/VA E 335         2 g                                                                           (active ingredient)                                      96° strength ethyl alcohol q.s.p.                                                           100 g                                                    ______________________________________                                    

The composition is limpid. When it has been introduced into a spraybottle, it is used as a hair lacquer.

PVP/VA E 335 denotes a vinylpyrrolidone/vinyl acetate (30/70) copolymer.

The commercial names and trade marks of the products used in theExamples represent the following products:

AMERCHOL L 101 Extract of lanolin alcohols sold by AMERCHOL

CETIOL LC Cetyl laurate sold by HENKEL

INDIPOL H 300 Polyisobutylene sold by AMOCO

STELLANOL M 32 Lanolin alcohols sold by STELLA

MIGLYOL 810 Triglycerides of saturated fatty acid (C8 to C12) ofvegetable origin sold by DYNAMIT NOBEL

ARGOBASE Lanolin derivatives sold by WEST BROOK LANOLIN COMPANY

NEW MEKON WHITE WAX Microcrystalline wax sold by RAFFINERIE FRANCAISED'OSOKERITE

SYNCROWAX E R L C Distearyl ester of glycol sold by CRODA

GAFQUAT 734 Quaternary vinylpyrrolidone copolymer of molecular weightabout 100,000 sold by GAF.

We claim:
 1. A hair dye composition comprising in an aqueous, alcoholicor aqueous alcoholic medium an effective amount of a hair dye to dyesaid hair and surface-active random oligomer having the formula

    R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H

wherein R₁ represents a linear or branched, saturated or unsaturatedaliphatic hydrocarbon radical, a cycloaliphatic radical, an aromaticradical or an alkyl aromatic radical, containing up to 30 carbon atoms,Z represents (i) a group having the formula, R₂ O--C₂ H₃ (A)--O]_(m) CH₂--, or (ii) a mixture of (i) and A, wherein A represents a non-ionic,cationic, anionic, or zwitterionic group, R₂ represents a linear orbranched, saturated or unsaturated aliphatic hydrocarbon radical, acycloaliphatic radical, an aromatic radical or an alkyl aromaticradical, containing 8 to 30 carbon atoms, n represents an averagestatistical value ranging from 1 to 20, and m represents an averagestatistical value ranging from 0.5 to
 10. 2. A hair dye compositioncomprising in an aqueous, alcoholic or aqueous alcoholic medium aneffective amount of a hair dye to dye said hair and a surface-activerandom oligomer having the formula

    R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H

wherein R₁ represents a linear or branched, saturated or unsaturatedaliphatic hydrocarbon radical, a cycloaliphatic radical, an aromaticradical or an alkyl aromatic radical, containing up to 30 carbon atoms,Z represents (i) a group having the formula, R₂ O--C₂ H₃ (A)--O]_(m) CH₂--, or (ii) a mixture of (i) and A, wherein A is selected form the groupconsisting of (a) --CH₂ OH, ##STR25## wherein u denotes 0 or 1,##STR26## wherein R₃ and R₄ each independently represent alkyl orhydroxyalkyl containing 1-3 carbon atoms; or R₃ and R₄ together with thenitrogen atom to which they are attached form a heterocycle having 5 or6 ring members, and u denotes 0 or 1, ##STR27## wherein HV denotes amineral or organic acid, and u, R₃ and R₄ having the meanings given in(c) above, ##STR28## wherein R₅ represents methyl, ethyl orhydroxyethyl, T.sup.⊖ denotes an anion, and u, R₃ and R₄ have themeanings given in (c), above, ##STR29## wherein Q.sup.⊖ represents CH₂COO⁻, CH₂ CH₂ COO⁻ or (CH₂)₃ SO₃ ⁻ and R₃ and R₄ have the meanings givenin (c), above, (g) --OSO₃ M wherein M denotes hydrogen or alkali metalor one equivalent of an alkaline earth metal, (h) --OCOCH₂ SO₃ M whereinM has the meaning given in (g), above, and ##STR30## wherein M has themeaning given in (g), above, and u denotes 0 or 1, R₂ represents alinear or branched, saturated or unsaturated aliphatic hydrocarbonradical, a cycloaliphatic radical, an aromatic radical or analkylaromatic radical, containing 8 to 30 carbon atoms, n represents anaverage statistical value ranging from 1 to 20, and m represents anaverage statistical value from 0.5 to
 10. 3. The hair dye composition ofclaim 1 wherein said surface-active random oligomer is present in anamount ranging from 0.2 to 80 percent by weight of said compositions. 4.A hair dye composition comprising in an aqueous, alcoholic or aqueousalcoholic medium an effective amount of a hair dye to dye said hair anda surface-active random oligomer having the formula

    R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H

wherein R₁ represents a mixture of C₈ H₁₇ and C₁₀ H₂₁, Z represents amixture of (i) CH₂ OH and (ii) R₂ O--C₂ H₃ (CH₂ OH)--O]_(m) CH₂ --wherein the ratio of (i):(ii) is 2:1 and R₂ represents a mixture of C₈H₁₇ and C₁₀ H₂₁, n represents an average statistical value of 9, and mrepresents an average statistical value of 0.5.
 5. The hair dyecomposition of claim 4 wherein said surface-active random oligomer ispresent in an amount ranging from 0.2 to 80 percent by weight of saidcomposition.
 6. A hair dye composition comprising in an aqueous,alcoholic or aqueous alcoholic medium an effective amount of a hair dyeto dye said hair and a surface-active random oligomer having the formula

    R.sub.1 --O--C.sub.2 H.sub.3 (Z)--O].sub.n H

wherein R₁ represents a linear or branched, saturated or unsaturatedaliphatic hydrocarbon radical, a cycloaliphatic radical, an aromaticradical or an alkyl aromatic radical, containing up to 30 carbon atoms,Z represents (i) a group having the formula, R₂ O--C₂ H₃ (A)--O]_(m) CH₂--, or (ii) a mixture of (i) and A, wherein A represents a non-ionic,cationic, anionic, or zwitterionic hydrophilic group, R₂ represents alinear or branched, saturated or unsaturated aliphatic hydrocarbonradical, a cycloaliphatic radical, an aromatic radical or an alkylaromatic radical, containing 8 to 30 carbon atoms, n represents anaverage statistical value ranging from 1 to 20, and m represents anaverage statistical value ranging from 0.5 to 10.